De-foaming spray dried catalyst slurries

ABSTRACT

A method for preparing a spray dried catalyst and a low viscosity, low foam spray dried catalyst system for olefin polymerization are provided. In one aspect, the method includes preparing a catalyst system including one or more components selected from metallocenes, non-metallocenes, and activators, adding mineral oil to the catalyst system to form a slurry, and adding one or more liquid alkanes having three or more carbon atoms to the slurry in an amount sufficient to reduce foaming and viscosity of the slurry. In one aspect, the catalyst system includes one or more catalysts selected from metallocenes, non-metallocenes, and a combination thereof, wherein the catalyst system is spray dried. The system further includes mineral oil to form a slurry including a catalyst system, and one or more liquid alkanes having three or more carbon atoms in an amount sufficient to reduce foaming and viscosity of the slurry.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of Ser. No. 10/780,522, filedFeb. 17, 2004, now abandoned, the disclosure of which is incorporated byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the present invention generally relate to a spray driedcatalyst slurry. More particularly, embodiments of the present inventionrelate to a spray died catalyst slurry for gas phase olefinpolymerization.

2. Description of the Related Art

A number of methodologies used for delivering catalysts to reactorsrequire the catalyst to be supported on an inert carrier such as silica.Impregnating a catalyst on a support has often been found to cause asignificant decrease in catalyst activity. In addition, large particles(>25 micrometers) of the support material have frequently been found inthe finished polymer product. These particles may adversely affectpolymer properties. This has been observed in film applications whereunexploded silica particles appear as defects or gels.

Spray-drying techniques have been employed as an alternative tosupported particles. Once a catalyst has been spray dried, the spraydried catalyst is added to a diluent to form a catalyst slurry andpumped to a polymerization reactor. A high solids concentration withinthe catalyst slurry is desirable to reduce the amount of slurry. Areduction in the amount of slurry reduces transportation expenses. Areduction in the amount of slurry also reduces the amount of diluentthat must be ultimately isolated and either discarded or recycled. Thisseparation process is timely and can greatly increase capital cost.

However, a high solids concentration typically increases the slurryviscosity. A high solids concentration also increases the amount offoaming which is typically generated by cooling gas during formation ofthe spray dried catalysts. A high slurry viscosity and foaming oftencause handling problems, storage problems as well as reactor injectionproblems.

There is a need, therefore, for a spray dried catalyst slurry that hasan increased solids content, a low viscosity, and a limited amount offoam.

SUMMARY OF THE INVENTION

A method for preparing a spray dried catalyst and a low viscosity, lowfoam spray dried catalyst system for olefin polymerization are provided.In one aspect, the method includes preparing a catalyst systemcomprising one or more components selected from the group consisting ofmetallocenes, non-metallocenes, and activators, adding mineral oil tothe catalyst system to form a slurry, and adding one or more liquidalkanes having three or more carbon atoms to the slurry in an amountsufficient to reduce foaming and viscosity of the slurry. In one aspect,the catalyst system includes one or more catalysts selected from thegroup consisting of metallocenes, non-metallocenes, and a combinationthereof, wherein the catalyst system is spray dried. The catalyst systemfurther includes mineral oil to form a slurry comprising the catalystsystem, and one or more liquid alkanes having three or more carbon atomsin an amount sufficient to reduce foaming and viscosity of the slurry.

Further, a method for olefin polymerization is provided. In one aspect,the method comprises preparing a catalyst system useful for olefinpolymerization, adding mineral oil to the catalyst system to form aslurry, adding one or more liquid alkanes having three or more carbonatoms to the slurry in an amount sufficient to reduce foaming andviscosity of the slurry, and transferring the slurry to a gas phasereactor.

The invention also provides for a method for preparing a catalyst,comprising: first combining mineral oil with one or more liquid alkaneshaving three or more carbon atoms to form a mixture; followed bycombining wit the mixture a spray dried catalyst system comprising oneor more components selected from the group consisting of metallocenes,non-metallocenes, and a combination thereof to form a slurry.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentinvention can be understood in detail, a more particular description ofthe invention, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this invention and are therefore not to beconsidered limiting of its scope, for the invention may admit to otherequally effective embodiments.

FIG. 1 is a schematic representation of an exemplary spray dry apparatussuitable for forming spray dried catalyst according to embodimentsdescribed herein.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

A spray dried catalyst slurry and a method for delivering the slurry toa polymerization reactor are provided. In one aspect, the spray driedcatalyst slurry includes mineral oil, at least one catalyst system, andone or more liquid alkanes having from three to twelve carbon atoms. Ithas been surprisingly found that the one or more liquid alkanes reducesthe viscosity of the slurry by at least 30 percent, and also reducesfoaming. Foaming is typically a result of evolved gas formed by areaction of volatile components and impurities within the catalystslurry, whereby this evolved gas forms a foam due to the surface tensionof the oil slurry.

The concentration of the components in the slurry is controlled toreduce the viscosity of the slurry and to reduce foaming. In one aspect,the spray dried catalyst slurry contains up to 20 percent by weight ofthe one or more liquid alkanes. In another aspect, the slurry containsup to 15 percent by weight of the one or more liquid alkanes. In yetanother aspect, the slurry contains up to 10 percent by weight of theone or more liquid alkanes. Preferably, the slurry contains betweenabout 2 percent by weight and 15 percent by weight of the one or moreliquid alkanes. More preferably, the slurry contains between about 2percent by weight and 10 percent by weight of the one or more liquidalkanes.

The concentration of the components in the slurry is also controlled tomaximize the amount of the catalyst system within the slurry. Due to thepresence of the liquid alkane, the slurry may contain up to 50 percentby weight of the catalyst system. In one aspect, the slurry contains atleast 10 percent by weight of the catalyst system. In another aspect,the slurry contains at least 15 percent by weight of the catalystsystem. In yet another aspect, the slurry contains at least 20 percentby weight of the catalyst system. Preferably, the slurry contains from 5percent by weight to about 35 percent by weight of the catalyst system.More preferably, the slurry contains from 10 percent by weight to about30 percent by weight of the catalyst system or from 15 percent by weightto about 25 percent by weight of the catalyst system.

The one or more liquid alkanes are preferably liquid underpolymerization conditions and relatively inert. Exemplary liquid alkanesinclude, but are not limited to, isopentane, hexane and heptane.Preferably, the liquid alkane is hexane.

The spray dried catalyst slurry preferably has a viscosity of from 300to 1,500 centipoise (cP), such as from 300 to 400 centipoise (cP) at 25°C. In one aspect, the spray dried catalyst slurry has a viscosity offrom 300 to 1,000 cP at 25° C. In another aspect, the spray driedcatalyst slurry has a viscosity of from 300 to 500 cP at 25° C. In yetanother aspect, the spray dried catalyst slurry has a viscosity of from300 to 400 cP at 25° C.

The spray dried catalyst slurry may be utilized in conjunction with anysuitable polymerization catalyst. Exemplary polymerization catalystsinclude, but are not limited to, metallocenes, Group 15 containingcompounds, phenoxide transition metal compositions, Group 5 or 6 metalimido complexes, bridged bis(arylamido) Group 4 compounds, derivativesthereof, and combinations thereof.

The term “catalyst system” may include any number of catalysts in anycombination as described herein, as well as any activator in anycombination as described herein. The term “catalyst” is usedinterchangeably with the term “catalyst component”, and includes anycompound or component, or combination of compounds or components, thatis capable of increasing the rate of a chemical reaction, such as thepolymerization or oligomerization of one or more olefins. As usedherein, in reference to Periodic Table “Groups” of Elements, the “new”numbering scheme for the Periodic Table Groups are used as in the CRCHandbook of Chemistry and Physics (David R. Lide ed., CRC Press 81st ed.2000).

In one aspect, the catalyst system is a mixed catalyst system of atleast one metallocene catalyst component and at least onenon-metallocene component. The mixed catalyst system may be described asa bimetallic catalyst composition or a multi-catalyst composition. Asused herein, the terms “bimetallic catalyst composition” and “bimetalliccatalyst” include any composition, mixture, or system that includes twoor more different catalyst components, each having a different metalgroup. The terms “multi-catalyst composition” and “multi-catalyst”include any composition, mixture, or system that includes two or moredifferent catalyst components regardless of the metals. Therefore, terms“bimetallic catalyst composition,” “bimetallic catalyst,”“multi-catalyst composition,” and “multi-catalyst” will be collectivelyreferred to herein as a “mixed catalyst system” unless specificallynoted otherwise.

Non-metallocene Component

Exemplary non-metallocene component include, but are not limited to, aGroup 15-containing catalyst. “Group 15-containing catalysts”, asreferred to herein, include Group 3 to Group 12 metal complexes, whereinthe metal is 2 to 4 coordinate and the coordinating moiety or moietiesinclude at least two Group 15 atoms, and up to four Group 15 atoms. Inone embodiment, the Group 15-containing catalyst is a complex of a Group4 metal and from one to four ligands such that the Group 4 metal is atleast 2 coordinate and the coordinating moiety or moieties include atleast two nitrogens.

In one embodiment, the Group 15-containing catalyst may include, but isnot limited to, Group 4 imino-phenol complexes, Group 4 bis(amide)complexes, and Group 4 pyridyl-amide complexes that are active towardsolefin polymerization to any extent. In another embodiment, the Group15-containing catalyst may be described by the following formula (I):α_(a)β_(b)γ_(g)MX_(n)  (I)

Each X is independently selected from halogen ions, hydrides, C₁ to C₁₂alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls, C₁ toC₁₂ alkoxys, C₆ to C₁₆ aryloxys, C₇ to C₁₈ alkylaryloxys, C₁ to C₁₂fluoroalkyls, C₆ to C₁₂ fluoroaryls, C₁ to C₁₂ heteroatom-containinghydrocarbons, halogenated C₆ to C₁₆ aryloxys, and substitutedderivatives thereof.

M is selected from Group 3 to Group 12 atoms in one embodiment; andselected from Group 3 to Group 10 atoms in a more particular embodiment;and selected from Group 3 to Group 6 atoms in yet a more particularembodiment; and selected from Ni, Cr, Ti, Zr and Hf in yet a moreparticular embodiment; and selected from Zr and Hf in yet a moreparticular embodiment.

Each β and γ are groups that each comprise at least one Group 14 toGroup 16 atom; and β (when present) and γ are groups bonded to M throughbetween 2 and 6 Group 14 to Group 16 atoms, at least two atoms beingGroup 15-containing atoms.

More particularly, β and γ are groups selected from Group 14 and Group15-containing: alkyls, aryls, alkylaryls, and heterocyclic hydrocarbons,and chemically bonded combinations thereof in one embodiment; andselected from Group 14 and Group 15-containing: C₁ to C₁₀ alkyls, C₆ toC₁₂ aryls, C₆ to C₁₈ alkylaryls, and C₄ to C₁₂ heterocyclichydrocarbons, and chemically bonded combinations thereof in a moreparticular embodiment; and selected from C₁ to C₁₀ alkylamines, C₁ toC₁₀ alkoxys, C₆ to C₂₀ alkylarylamines, C₆ to C₁₈ alkylaryloxys, and C₄to C₁₂ nitrogen containing heterocyclic hydrocarbons, and C₄ to C₁₂alkyl substituted nitrogen containing heterocyclic hydrocarbons andchemically bonded combinations thereof in yet a more particularembodiment; and selected from anilinyls, pyridyls, quinolyls, pyrrolyls,pyrimidyls, purinyls, imidazyls, indolyls, C₁ to C₆ alkyl substitutedgroups selected from anilinyls, pyridyls, quinolyls, pyrrolyls,pyrimidyls, purinyls, imidazyls, indolyls; C₁ to C₆ alkylaminesubstituted groups selected from anilinyls, pyridyls, quinolyls,pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls, amine substitutedanilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls,imidazyls, and indolyls; hydroxy substituted groups selected fromanilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls,imidazyls, and indolyls; methyl-substituted phenylamines, and chemicallybonded combinations thereof in yet a more particular embodiment;

Each α is a linking (or “bridging”) moiety that, when present, forms achemical bond to each of β and γ, or two γ's, thus forming a “γαγ” or“γαβ” ligand bound to M; α may also comprise a Group 14 to Group 16 atomwhich may be bonded to M through the Group 14 to Group 16 atom in oneembodiment; and more particularly, α is a divalent bridging groupselected from alkylenes, arylenes, alkenylenes, heterocyclic arylenes,alkylarylenes, heteroatom containing alkylenes, heteroatom containingalkenylenes and heterocyclic hydrocarbonylenes in one embodiment; andselected from C₁ to C₁₀ alkylenes, C₂ to C₁₀ alkenylenes, C₆ to C₁₂arylenes, C₁ to C₁₀ divalent ethers, C₆ to C₁₂ O— or N-containingarylenes, C₂ to C₁₀ alkyleneamines, C₆ to C₁₂ aryleneamines, andsubstituted derivatives thereof in yet a more particular embodiment;

a is an integer from 0 to 2; a is either 0 or 1 in a more particularembodiment; and a is 1 in yet a more particular embodiment; b is aninteger from 0 to 2; g is an integer from 1 to 2; wherein in oneembodiment, a is 1, b is 0 and g is 2; and

n is an integer from 0 to 4 in one embodiment; and an integer from 1 to3 in a more particular embodiment; and an integer from 2 to 3 in yet amore particular embodiment.

As used herein, “chemically bonded combinations thereof” means thatadjacent groups, (β and γ groups) may form a chemical bond between them.In one embodiment, the β and γ groups are chemically bonded through oneor more α groups there between.

As used herein, the terms “alkyleneamines” and “aryleneamines” describealkylamines and arylamines (respectively) that are deficient by twohydrogens, thus forming chemical bonds with two adjacent γ groups, oradjacent β and γ groups. Thus, an example of an alkyleneamine is—CH₂CH₂N(CH₃)CH₂CH₂—, and an example of a heterocyclic hydrocarbylene oraryleneamine is —C₅H₃N— (divalent pyridine). An “alkylene-arylamine” isa group such as, for example, —CH₂CH₂(C₅H₃N)CH₂CH₂—.

In yet another embodiment, the Group 15-containing catalyst may berepresented by the structures (II) and (III):

wherein E and Z are Group 15 elements independently selected fromnitrogen and phosphorus in one embodiment; and nitrogen in a moreparticular embodiment;

L is selected from Group 15 atoms, Group 16 atoms, Group 15-containinghydrocarbylenes and a Group 16 containing hydrocarbylenes in oneembodiment; wherein R³ is absent when L is a Group 16 atom; in yet amore particular embodiment, when R³ is absent, L is selected fromheterocyclic hydrocarbylenes; and in yet a more particular embodiment, Lis selected from nitrogen, phosphorous, anilinyls, pyridyls, quinolyls,pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls; C₁ to C₆ alkylsubstituted groups selected from anilinyls, pyridyls, quinolyls,pyrrolyls, pyrimidyls, purinyls, imidazyls, and indolyls; C₁ to C₆alkylamine substituted groups selected from anilinyls, pyridyls,quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls; aminesubstituted anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls,purinyls, imidazyls, and indolyls; hydroxy substituted groups selectedfrom anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls,imidazyls, and indolyls; methyl-substituted phenylamines, substitutedderivatives thereof, and chemically bonded combinations thereof;

L′ is selected from Group 15 atoms, Group 16 atoms, and Group 14 atomsin one embodiment; and selected from Group 15 and Group 16 atoms in amore particular embodiment; and is selected from groups as defined by Labove in yet a more particular embodiment, wherein “EZL” and “EZL′” maybe referred to as a “ligand”, the EZL and EZL′ ligands comprising the R*and R¹–R⁷ groups;

L and L′ may or may not form a bond with M;

y is an integer ranging from 0 to 2 (when y is 0, group L′, *R and R³are absent);

M is selected from Group 3 to Group 5 atoms, Group 4 atoms in a moreparticular embodiment, and selected from Zr and Hf in yet a moreparticular embodiment;

n is an integer ranging from 1 to 4 in one embodiment; n is an integerranging from 2 to 3 in a more particular embodiment;

R¹ and R² are independently: divalent bridging groups selected fromalkylenes, arylenes, heteroatom containing alkylenes, heteroatomcontaining arylenes, substituted alkylenes, substituted arylenes andsubstituted heteroatom containing alkylenes, wherein the heteroatom isselected from silicon, oxygen, nitrogen, germanium, phosphorous, boronand sulfur in one embodiment; selected from C₁ to C₂₀ alkylenes, C₆ toC₁₂ arylenes, heteroatom-containing C₁ to C₂₀ alkylenes andheteroatom-containing C₆ to C₁₂ arylenes in a more particularembodiment; and in yet a more particular embodiment selected from —CH₂—,—C(CH₃)₂—, —C(C₆H₅)₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —Si(CH₃)₂—, —Si(CH₆H₅)₂—,—C₆H₁₀—, —C₆H₄—, and substituted derivatives thereof, the substitutionsincluding C₁ to C₄ alkyls, phenyl, and halogen radicals;

R³ is absent in one embodiment; a group selected from hydrocarbylgroups, hydrogen radical, halogen radicals, and heteroatom-containinggroups in a more particular embodiment; and selected from linear alkyls,cyclic alkyls, and branched alkyls having 1 to 20 carbon atoms in yet amore particular embodiment;

*R is absent in one embodiment; a group selected from hydrogen radical,Group 14 atom containing groups, halogen radicals, and aheteroatom-containing groups in yet a more particular embodiment;

R⁴ and R⁵ are independently: groups selected from alkyls, aryls,substituted aryls, cyclic alkyls, substituted cyclic alkyls, cyclicarylalkyls, substituted cyclic arylalkyls and multiple ring systems inone embodiment, each group having up to 20 carbon atoms, and between 3and 10 carbon atoms in a more particular embodiment; selected from C₁ toC₂₀ alkyls, C₁ to C₂₀ aryls, C₁ to C₂₀ arylalkyls, andheteroatom-containing groups (for example PR₃, where R is an alkylgroup) in yet a more particular embodiment; and

R⁶ and R⁷ are independently: absent in one embodiment; groups selectedfrom hydrogen radicals, halogen radicals, heteroatom-containing groupsand hydrocarbyls in a more particular embodiment; selected from linear,cyclic and branched alkyls having from 1 to 20 carbon atoms in yet amore particular embodiment;

R¹ and R² may be associated with one another, and/or R⁴ and R⁵ may beassociated with one another as through a chemical bond.

Described yet more particularly, the Group 15-containing catalyst can bedescribed as the embodiments shown in structures (IV), (V) and (VI)(where “N” is nitrogen):

The structure (IV) represents pyridyl-amide structures, structure (V)represents imino-phenol structures, and structure (VI) representsbis(amide) structures;

w is an integer from 1 to 3, and 1 or 2 in a more particular embodiment,and 1 in yet a more particular embodiment;

M is a Group 3 to Group 13 element, a Group 3 to Group 6 element in amore particular embodiment, and a Group 4 element in yet a moreparticular embodiment; and

n is an integer ranging from 0 to 4, and from 1 to 3 in a moreparticular embodiment, and from 2 to 3 in yet a more particularembodiment, and 2 in yet a more particular embodiment.

Each X is independently selected from halogen ions, hydrides, C₁ to C₁₂alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls, C₁ toC₁₂ alkoxys, C₆ to C₁₆ aryloxys, C₇ to C₁₈ alkylaryloxys, C₁ to C₁₂fluoroalkyls, C₆ to C₁₂ fluoroaryls, C₁ to C₁₂ heteroatom-containinghydrocarbons, halogenated C₆ to C₁₆ aryloxys, and substitutedderivatives thereof.

In structures (IV), (V), and (VI), R¹′ is selected from hydrocarbylenesand heteroatom-containing hydrocarbylenes in one embodiment, andselected from —SiR₂—, alkylenes, arylenes, alkenylenes and substitutedalkylenes, substituted alkenylenes and substituted arylenes in anotherembodiment; and selected from —SiR₂—, C₁ to C₆ alkylenes, C₆ to C₁₂arylenes, C₁ to C₆ substituted alkylenes and C₆ to C₁₂ substitutedarylenes in another embodiment.

R is selected from C₁ to C₆ alkyls and C₆ to C₁₂ aryls; and R²′, R³′,R⁴′, R⁵′, R⁶′ and R* are independently selected from hydride, C₁ to C₁₀alkyls, C₆ to C₁₂ aryls, C₆ to C₁₈ alkylaryls, C₄ to C₁₂ heterocyclichydrocarbyls, substituted C₁ to C₁₀ alkyls, substituted C₆ to C₁₂ aryls,substituted C₆ to C₁₈ alkylaryls, and substituted C₄ to C₁₂ heterocyclichydrocarbyls and chemically bonded combinations thereof in oneembodiment.

R* is absent in a particular embodiment; and in another embodiment, R*—Nrepresents a nitrogen containing group or ring such as a pyridyl groupor a substituted pyridyl group that is bridged by the R¹′ groups. In yetanother embodiment, R*—N is absent, and the R¹′ groups form a chemicalbond to one another.

In one embodiment of structures (IV), (V), and (VI), R¹′ is selectedfrom methylene, ethylene, 1-propylene, 2-propylene, ═Si(CH₃)₂,═Si(phenyl)₂, —CH═, —C(CH₃)═, —C(phenyl)₂—, —C(phenyl)═ (wherein “═”represents two chemical bonds), and the like.

In a particular embodiment of structure (V), R²′ and R⁴′ are selectedfrom 2-methylphenyl, 2-n-propylphenyl, 2-iso-propylphenyl,2-iso-butylphenyl, 2-tert-butylphenyl, 2-fluorophenyl, 2-chlorophenyl,2-bromophenyl, 2-methyl-4-chlorophenyl, 2-n-propyl-4-chlorophenyl,2-iso-propyl-4-chlorophenyl, 2-iso-butyl-4-chlorophenyl,2-tert-butyl-4-chlorophenyl, 2-methyl-4-fluorophenyl,2-n-propyl-4-fluorophenyl, 2-iso-propyl-4-fluorophenyl,2-iso-butyl-4-fluorophenyl, 2-tert-butyl-4-fluorophenyl,2-methyl-4-bromophenyl, 2-n-propyl-4-bromophenyl,2-iso-propyl-4-bromophenyl, 2-iso-butyl-4-bromophenyl,2-tert-butyl-4-bromophenyl, and the like.

In yet another particular embodiment of structures (IV) and (VI), R²′and R³′ are selected from 2-methylphenyl, 2-n-propylphenyl,2-iso-propylphenyl, 2-iso-butylphenyl, 2-tert-butylphenyl,2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 4-methylphenyl,4-n-propylphenyl, 4-iso-propylphenyl, 4-iso-butylphenyl,4-tert-butylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl,6-methylphenyl, 6-n-propylphenyl, 6-iso-propylphenyl, 6-iso-butylphenyl,6-tert-butylphenyl, 6-fluorophenyl, 6-chlorophenyl, 6-bromophenyl,2,6-dimethylphenyl, 2,6-di-n-propylphenyl, 2,6-di-iso-propylphenyl,2,6-di-isobutylphenyl, 2,6-di-tert-butylphenyl, 2,6-difluorophenyl,2,6-dichlorophenyl, 2,6-dibromophenyl, 2,4,6-trimethylphenyl,2,4,6-tri-n-propylphenyl, 2,4,6-tri-iso-propylphenyl,2,4,6-tri-iso-butylphenyl, 2,4,6-tri-tert-butylphenyl,2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl,2,3,4,5,6-pentafluorophenyl, 2,3,4,5,6-pentachlorophenyl,2,3,4,5,6-pentabromophenyl, and the like.

In another embodiment of structures (IV), (V), and (VI), X isindependently selected from fluoride, chloride, bromide, methyl, ethyl,phenyl, benzyl, phenyloxy, benzloxy, 2-phenyl-2-propoxy,1-phenyl-2-propoxy, 1-phenyl-2-butoxy, 2-phenyl-2-butoxy and the like.

As used herein, “chemically bonded combinations” means that adjacentgroups may form a chemical bond between them, thus forming a ringsystem, either saturated, partially unsaturated, or aromatic.

Non-limiting examples of the Group 15-containing catalyst arerepresented by the structures (VIIa)–(VIIf) (where “N” is nitrogen):

In structures (VIIa) through (VIIf) M is selected from Group 4 atoms inone embodiment; and M is selected from Zr and Hf in a more particularembodiment;

n is an integer ranging from 0 to 4, and from 2 to 3 in a moreparticular embodiment; and

R¹ through R¹¹ in structures (VIIa) through (VIIf) are selected fromhydride, fluorine radical, chlorine radical, bromine radical, methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and phenyl.

Each X is independently selected from halogen ions, hydrides, C₁ to C₁₂alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls, C₁ toC₁₂ alkoxys, C₆ to C₁₆ aryloxys, C₇ to C₁₈ alkylaryloxys, C₁ to C₁₂fluoroalkyls, C₆ to C₁₂ fluoroaryls, C₁ to C₁₂ heteroatom-containinghydrocarbons, halogenated C₆ to C₁₆ aryloxys, and substitutedderivatives thereof. Preferably, at least one X is a halogenated aryloxygroup or a derivative thereof. More preferably, at least one X is apentafluorophenoxy group.

Metallocene Catalyst Component

Exemplary metallocene catalyst components include, but are not limitedto, “half sandwich” and “full sandwich” compounds having one or more Cpligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl)bound to at least one Group 3 to Group 12 metal atom, and one or moreleaving group(s) bound to the at least one metal atom. Hereinafter,these compounds will be referred to as “metallocenes” or “metallocenecatalyst components”.

The Cp ligands are one or more rings or ring system(s), at least aportion of which includes π-bonded systems, such as cycloalkadienylligands and heterocyclic analogues. The ring(s) or ring system(s)typically comprise atoms selected from the group consisting of Groups 13to 16 atoms, and more particularly, the atoms that make up the Cpligands are selected from the group consisting of carbon, nitrogen,oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum andcombinations thereof, wherein carbon makes up at least 50% of the ringmembers. Even more particularly, the Cp ligand(s) are selected from thegroup consisting of substituted and unsubstituted cyclopentadienylligands and ligands isolobal to cyclopentadienyl, non-limiting examplesof which include cyclopentadienyl, indenyl, fluorenyl and otherstructures. Further non-limiting examples of such ligands includecyclopentadienyl, cyclopentaphenanthreneyl, indenyl, benzindenyl,fluorenyl, octahydrofluorenyl, cyclooctatetraenyl,cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl,9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7H-dibenzofluorenyl,indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl,hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or“H₄Ind”), substituted versions thereof (as described in more detailbelow), and heterocyclic versions thereof.

The metal atom “M” of the metallocene catalyst compound, as describedthroughout the specification and claims, may be selected from the groupconsisting of Groups 3 through 12 atoms and lanthanide Group atoms inone embodiment; and selected from the group consisting of Groups 3through 10 atoms in a more particular embodiment, and selected from thegroup consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co,Rh, Ir, and Ni in yet a more particular embodiment; and selected fromthe group consisting of Groups 4, 5 and 6 atoms in yet a more particularembodiment, and a Ti, Zr, Hf atoms in yet a more particular embodiment,and Zr in yet a more particular embodiment. The oxidation state of themetal atom “M” may range from 0 to +7 in one embodiment; and in a moreparticular embodiment, is +1, +2, +3, +4 or +5; and in yet a moreparticular embodiment is +2, +3 or +4. The groups bound the metal atom“M” are such that the compounds described below in the formulas andstructures are neutral, unless otherwise indicated. The Cp ligand(s)form at least one chemical bond with the metal atom M to form the“metallocene catalyst compound”. The Cp ligands are distinct from theleaving groups bound to the catalyst compound in that they are nothighly susceptible to substitution/abstraction reactions.

In one aspect, the one or more metallocene catalyst components arerepresented by the formula (II):Cp^(A)Cp^(B)MX_(n)  (VIII)

wherein M is as described above; each X is chemically bonded to M; eachCp group is chemically bonded to M; and n is 0 or an integer from 1 to4, and either 1 or 2 in a particular embodiment.

The ligands represented by Cp^(A) and Cp^(B) in formula (VIII) may bethe same or different cyclopentadienyl ligands or ligands isolobal tocyclopentadienyl, either or both of which may contain heteroatoms andeither or both of which may be substituted by a group R. In oneembodiment, Cp^(A) and Cp^(B) are independently selected from the groupconsisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl,and substituted derivatives of each.

Independently, each Cp^(A) and Cp^(B) of formula (VIII) may beunsubstituted or substituted with any one or combination of substituentgroups R. Non-limiting examples of substituent groups R as used instructure (II) include hydrogen radicals, alkyls, alkenyls, alkynyls,cycloalkyls, aryls, acyls, aroyls, alkoxys, aryloxys, alkylthiols,dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls,carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos,aroylaminos, and combinations thereof.

More particular non-limiting examples of alkyl substituents R associatedwith formula (II) includes methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, andtert-butylphenyl groups and the like, including all their isomers, forexample tertiary-butyl, isopropyl, and the like. Other possible radicalsinclude substituted alkyls and aryls such as, for example, fluoromethyl,fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl andhydrocarbyl substituted organometalloid radicals includingtrimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; andhalocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstituted boron radicalsincluding dimethylboron for example; and disubstituted Group 15 radicalsincluding dimethylamine, dimethylphosphine, diphenylamine,methylphenylphosphine, Group 16 radicals including methoxy, ethoxy,propoxy, phenoxy, methylsulfide and ethylsulfide. Other substituents Rinclude olefins such as but not limited to olefinically unsaturatedsubstituents including vinyl-terminated ligands, for example 3-butenyl,2-propenyl, 5-hexenyl and the like. In one embodiment, at least two Rgroups, two adjacent R groups in one embodiment, are joined to form aring structure having from 3 to 30 atoms selected from the groupconsisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium,aluminum, boron and combinations thereof. Also, a substituent group Rgroup such as 1-butanyl may form a bonding association to the element M.

Each X in formula (VIII) is independently selected from the following:halogen ions, hydrides, C₁ to C₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂aryls, C₇ to C₂₀ alkylaryls, C₁ to C₁₂ alkoxys, C₆ to C₁₆ aryloxys, C₇to C₁₈ alkylaryloxys, C₁ to C₁₂ fluoroalkyls, C₆ to C₁₂ fluoroaryls, andC₁ to C₁₂ heteroatom-containing hydrocarbons and substituted derivativesthereof in a more particular embodiment; hydride, halogen ions, C₁ to C₆alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈ alkylaryls, C₁ to C₆ alkoxys, C₆ toC₁₄ aryloxys, C₇ to C₁₆ alkylaryloxys, C₁ to C₆ alkylcarboxylates, C₁ toC₆ fluorinated alkylcarboxylates, C₆ to C₁₂ arylcarboxylates, C₇ to C₁₈alkylarylcarboxylates, C₁ to C₆ fluoroalkyls, C₂ to C₆ fluoroalkenyls,and C₇ to C₁₈ fluoroalkylaryls in yet a more particular embodiment;hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl,fluoromethyls and fluorophenyls in yet a more particular embodiment; C₁to C₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀alkylaryls, substituted C₁ to C₁₂ alkyls, substituted C₆ to C₁₂ aryls,substituted C₇ to C₂₀ alkylaryls and C₁ to C₁₂ heteroatom-containingalkyls, C₁ to C₁₂ heteroatom-containing aryls and C₁ to C₁₂heteroatom-containing alkylaryls in yet a more particular embodiment;chloride, fluoride, C₁ to C₆ alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈alkylaryls, halogenated C₁ to C₆ alkyls, halogenated C₂ to C₆ alkenyls,and halogenated C₇ to C₁₈ alkylaryls in yet a more particularembodiment; fluoride, methyl, ethyl, propyl, phenyl, methylphenyl,dimethylphenyl, trimethylphenyl, fluoromethyls (mono-, di- andtrifluoromethyls) and fluorophenyls (mono-, di-, tri-, tetra- andpentafluorophenyls) in yet a more particular embodiment.

Other non-limiting examples of X groups in formula (VIII) includeamines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicalshaving from 1 to 20 carbon atoms, fluorinated hydrocarbon radicals(e.g., —C₆F₅ (pentafluorophenyl)), fluorinated alkylcarboxylates (e.g.,CF₃C(O)O—), hydrides and halogen ions and combinations thereof. Otherexamples of X ligands include alkyl groups such as cyclobutyl,cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike. In one embodiment, two or more X's form a part of a fused ring orring system.

In another aspect, the metallocene catalyst component includes those offormula (VIII) where Cp^(A) and Cp^(B) are bridged to each other by atleast one bridging group, (A), such that the structure is represented byformula (IX):Cp^(A)(A)Cp^(B)MX_(n)  (IX)

These bridged compounds represented by formula (IX) are known as“bridged metallocenes”. Cp^(A), Cp^(B), M, X and n are as defined abovefor formula (VIII); and wherein each Cp ligand is chemically bonded toM, and (A) is chemically bonded to each Cp. Non-limiting examples ofbridging group (A) include divalent hydrocarbon groups containing atleast one Group 13 to 16 atom, such as but not limited to at least oneof a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium andtin atom and combinations thereof; wherein the heteroatom may also be C₁to C₁₂ alkyl or aryl substituted to satisfy neutral valency. Thebridging group (A) may also contain substituent groups R as definedabove for formula (VIII) including halogen radicals and iron. Moreparticular non-limiting examples of bridging group (A) are representedby C₁ to C₆ alkylenes, substituted C₁ to C₆ alkylenes, oxygen, sulfur,R′₂C═, R′₂Si═, —Si(R′)₂Si(R′₂)—, R′₂Ge═, R′P═ (wherein “═” representstwo chemical bonds), where R′ is independently selected from the groupconsisting of hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, hydrocarbyl-substituted organometalloid,halocarbyl-substituted organometalloid, disubstituted boron,disubstituted Group 15 atoms, substituted Group 16 atoms, and halogenradical; and wherein two or more R′ may be joined to form a ring or ringsystem. In one embodiment, the bridged metallocene catalyst component offormula (IX) has two or more bridging groups (A).

Other non-limiting examples of bridging group (A) include methylene,ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene,1,2-dimethylethylene, 1,2-diphenylethylene, 1,1,2,2-tetramethylethylene,dimethylsilyl, diethylsilyl, methyl-ethylsilyl,trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl,di(n-propyl)silyl, di(i-propyl)silyl, di(n-hexyl)silyl,dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl,t-butylcyclohexylsilyl, di(t-butylphenyl)silyl, di(p-tolyl)silyl and thecorresponding moieties wherein the Si atom is replaced by a Ge or a Catom; dimethylsilyl, diethylsilyl, dimethylgermyl and diethylgermyl.

In another embodiment, bridging group (A) may also be cyclic,comprising, for example 4 to 10, 5 to 7 ring members in a moreparticular embodiment. The ring members may be selected from theelements mentioned above, from one or more of B, C, Si, Ge, N and O in aparticular embodiment. Non-limiting examples of ring structures whichmay be present as or part of the bridging moiety are cyclobutylidene,cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene andthe corresponding rings where one or two carbon atoms are replaced by atleast one of Si, Ge, N and O, in particular, Si and Ge. The bondingarrangement between the ring and the Cp groups may be either cis-,trans-, or a combination.

The cyclic bridging groups (A) may be saturated or unsaturated and/orcarry one or more substituents and/or be fused to one or more other ringstructures. If present, the one or more substituents are selected fromthe group consisting of hydrocarbyl (e.g., alkyl such as methyl) andhalogen (e.g., F, Cl) in one embodiment. The one or more Cp groups whichthe above cyclic bridging moieties may optionally be fused to may besaturated or unsaturated and are selected from the group consisting ofthose having 4 to 10, more particularly 5, 6 or 7 ring members (selectedfrom the group consisting of C, N, O and S in a particular embodiment)such as, for example, cyclopentyl, cyclohexyl and phenyl. Moreover,these ring structures may themselves be fused such as, for example, inthe case of a naphthyl group. Moreover, these (optionally fused) ringstructures may carry one or more substituents. Illustrative,non-limiting examples of these substituents are hydrocarbyl(particularly alkyl) groups and halogen atoms.

The ligands Cp^(A) and Cp^(B) of formula (VIII) and (IX) are differentfrom each other in one embodiment, and the same in another embodiment.

In yet another aspect, the metallocene catalyst components includemono-ligand metallocene compounds (e.g., mono cyclopentadienyl catalystcomponents) such as described in WO 93/08221 for example. In thisembodiment, the at least one metallocene catalyst component is a bridged“half-sandwich” metallocene represented by the formula (X):Cp^(A)(A)QMX_(n)  (X)

wherein Cp^(A) is defined above and is bound to M; (A) is a bridginggroup bonded to Q and Cp^(A); and wherein an atom from the Q group isbonded to M; and n is 0 or an integer from 1 to 3; 1 or 2 in aparticular embodiment. In formula (X), Cp^(A), (A) and Q may form afused ring system. The X groups and n of formula (X) are as definedabove in formula (VIII) and (IX). In one embodiment, Cp^(A) is selectedfrom the group consisting of cyclopentadienyl, indenyl,tetrahydroindenyl, fluorenyl, substituted versions thereof, andcombinations thereof.

In formula (X), Q is a heteroatom-containing ligand in which the bondingatom (the atom that is bonded with the metal M) is selected from thegroup consisting of Group 15 atoms and Group 16 atoms in one embodiment,and selected from the group consisting of nitrogen, phosphorus, oxygenor sulfur atom in a more particular embodiment, and nitrogen and oxygenin yet a more particular embodiment. Non-limiting examples of Q groupsinclude alkylamines, arylamines, mercapto compounds, ethoxy compounds,carboxylates (e.g., pivalate), carbamates, azenyl, azulene, pentalene,phosphoyl, phosphinimine, pyrrolyl, pyrozolyl, carbazolyl, borabenzeneother compounds comprising Group 15 and Group 16 atoms capable ofbonding with M.

In yet another aspect, the at least one metallocene catalyst componentis an unbridged “half sandwich” metallocene represented by the formula(XI):Cp^(A)MQ_(q)X_(n)  (XI)

wherein Cp^(A) is defined as for the Cp groups in (VIII) and is a ligandthat is bonded to M; each Q is independently bonded to M; Q is alsobound to Cp^(A) in one embodiment; X is a leaving group as describedabove in (VIII); n ranges from 0 to 3, and is 1 or 2 in one embodiment;q ranges from 0 to 3, and is 1 or 2 in one embodiment. In oneembodiment, Cp^(A) is selected from the group consisting ofcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substitutedversion thereof, and combinations thereof.

In formula (XI), Q is selected from the group consisting of ROO⁻, RO—,R(O)—, —NR—, —CR₂—, —S—, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, —H, andsubstituted and unsubstituted aryl groups, wherein R is selected fromthe group consisting of C₁ to C₆ alkyls, C₆ to C₁₂ aryls, C₁ to C₆alkylamines, C₆ to C₁₂ alkylarylamines, C₁ to C₆ alkoxys, C₆ to C₁₂aryloxys, and the like. Non-limiting examples of Q include C₁ to C₁₂carbamates, C₁ to C₁₂ carboxylates (e.g., pivalate), C₂ to C₂₀ allyls,and C₂ to C₂₀ heteroallyl moieties.

Described another way, the “half sandwich” metallocenes above can bedescribed for example, U.S. Pat. No. 6,069,213:Cp^(A)M(Q₂GZ)X_(n) or T(Cp^(A)M(Q₂GZ)X_(n))_(m)  (XII)

wherein M, Cp^(A), X and n are as defined above;

Q₂GZ forms a polydentate ligand unit (e.g., pivalate), wherein at leastone of the Q groups form a bond with M, and is defined such that each Qis independently selected from the group consisting of —O—, —NR—, CR₂—and —S—; G is either carbon or silicon; and Z is selected from the groupconsisting of R, —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, and hydride,providing that when Q is —NR—, then Z is selected from the groupconsisting of —OR, —NR₂, —SR, —SiR₃, —PR₂; and provided that neutralvalency for Q is satisfied by Z; and wherein each R is independentlyselected from the group consisting of C₁ to C₁₀ heteroatom containinggroups, C₁ to C₁₀ alkyls, C₆ to C₁₂ aryls, C₆ to C₁₂ alkylaryls, C₁ toC₁₀ alkoxys, and C₆ to C₁₂ aryloxys;

n is 1 or 2 in a particular embodiment; and

T is a bridging group selected from the group consisting of C₁ to C₁₀alkylenes, C₆ to C₁₂ arylenes and C₁ to C₁₀ heteroatom containinggroups, and C₆ to C₁₂ heterocyclic groups; wherein each T group bridgesadjacent “Cp^(A)M(Q₂GZ)X_(n)” groups, and is chemically bonded to theCp^(A) groups.

m is an integer from 1 to 7; m is an integer from 2 to 6 in a moreparticular embodiment.

In another aspect, the at least one metallocene catalyst component canbe described more particularly in structures (XIIIa), (XIIIb), (XIIIc),(XIIId), (XIIIe), and (XIIIf):

wherein in structures (XIIIa) to (XIIIf), M is selected from the groupconsisting of Group 3 to Group 12 atoms, and selected from the groupconsisting of Group 3 to Group 10 atoms in a more particular embodiment,and selected from the group consisting of Group 3 to Group 6 atoms inyet a more particular embodiment, and selected from the group consistingof Group 4 atoms in yet a more particular embodiment, and selected fromthe group consisting of Zr and Hf in yet a more particular embodiment;and is Zr in yet a more particular embodiment;

wherein Q in (XIIIa) to (XIIIf) is selected from the group consisting ofalkylenes, aryls, arylenes, alkoxys, aryloxys, amines, arylamines (e.g.,pyridyl) alkylamines, phosphines, alkylphosphines, substituted alkyls,substituted aryls, substituted alkoxys, substituted aryloxys,substituted amines, substituted alkylamines, substituted phosphines,substituted alkylphosphines, carbamates, heteroallyls, carboxylates(non-limiting examples of suitable carbamates and carboxylates includetrimethylacetate, trimethylacetate, methylacetate, p-toluate, benzoate,diethylcarbamate, and dimethylcarbamate), fluorinated alkyls,fluorinated aryls, and fluorinated alkylcarboxylates; wherein thesaturated groups defining Q comprise from 1 to 20 carbon atoms in oneembodiment; and wherein the aromatic groups comprise from 5 to 20 carbonatoms in one embodiment;

wherein each R* is independently: selected from the group consisting ofhydrocarbylenes and heteroatom-containing hydrocarbylenes in oneembodiment; and selected from the group consisting of alkylenes,substituted alkylenes and heteroatom-containing hydrocarbylenes inanother embodiment; and selected from the group consisting of C₁ to C₁₂alkylenes, C₁ to C₁₂ substituted alkylenes, and C₁ to C₁₂heteroatom-containing hydrocarbylenes in a more particular embodiment;and selected from the group consisting of C₁ to C₄ alkylenes in yet amore particular embodiment; and wherein both R* groups are identical inanother embodiment in structures (XIIIf);

A is as described above for (A) in structure (IX), and moreparticularly, selected from the group consisting of a chemical bond,—O—, —S—, —SO₂—, —NR—, ═SiR₂, ═GeR₂, ═SnR₂, —R₂SiSiR₂—, RP═, C₁ to C₁₂alkylenes, substituted C₁ to C₁₂ alkylenes, divalent C₄ to C₁₂ cyclichydrocarbons and substituted and unsubstituted aryl groups in oneembodiment; and selected from the group consisting of C₅ to C₈ cyclichydrocarbons, —CH₂CH₂—, ═CR₂ and ═SiR₂ in a more particular embodiment;wherein and R is selected from the group consisting of alkyls,cycloalkyls, aryls, alkoxys, fluoroalkyls and heteroatom-containinghydrocarbons in one embodiment; and R is selected from the groupconsisting of C₁ to C₆ alkyls, substituted phenyls, phenyl, and C₁ to C₆alkoxys in a more particular embodiment; and R is selected from thegroup consisting of methoxy, methyl, phenoxy, and phenyl in yet a moreparticular embodiment;

wherein A may be absent in yet another embodiment, in which case each R*is defined as for R¹–R¹³;

each X is as described above in (VIII);

n is an integer from 0 to 4, and from 1 to 3 in another embodiment, and1 or 2 in yet another embodiment; and

R¹ through R¹³ are independently: selected from the group consisting ofhydrogen radical, halogen radicals, C₁ to C₁₂ alkyls, C₂ to C₁₂alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls, C₁ to C₁₂ alkoxys, C₁to C₁₂ fluoroalkyls, C₆ to C₁₂ fluoroaryls, and C₁ to C₁₂heteroatom-containing hydrocarbons and substituted derivatives thereofin one embodiment; selected from the group consisting of hydrogenradical, fluorine radical, chlorine radical, bromine radical, C₁ to C₆alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈ alkylaryls, C₁ to C₆ fluoroalkyls,C₂ to C₆ fluoroalkenyls, C₇ to C₁₈ fluoroalkylaryls in a more particularembodiment; and hydrogen radical, fluorine radical, chlorine radical,methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl,hexyl, phenyl, 2,6-di-methylpheyl, and 4-tertiarybutylpheyl groups inyet a more particular embodiment; wherein adjacent R groups may form aring, either saturated, partially saturated, or completely saturated.

The structure of the metallocene catalyst component represented by(XIIIa) may take on many forms such as disclosed in, for example, U.S.Pat. No. 5,026,798, U.S. Pat. No. 5,703,187, and U.S. Pat. No.5,747,406, including a dimmer or oligomeric structure, such as disclosedin, for example, U.S. Pat. No. 5,026,798 and U.S. Pat. No. 6,069,213.

In a particular embodiment of the metallocene represented in (XIIId), R¹and R² form a conjugated 6-membered carbon ring system that may or maynot be substituted.

Non-limiting examples of metallocene catalyst components consistent withthe description herein include:

-   cyclopentadienylzirconium X_(n),-   indenylzirconium X_(n),-   (1-methylindenyl)zirconium X_(n),-   (2-methylindenyl)zirconium X_(n),-   (1-propylindenyl)zirconium X_(n),-   (2-propylindenyl)zirconium X_(n),-   (1-butylindenyl)zirconium X_(n),-   (2-butylindenyl)zirconium X_(n),-   (methylcyclopentadienyl)zirconium X_(n),-   tetrahydroindenylzirconium X_(n),-   (pentamethylcyclopentadienyl)zirconium X_(n),-   cyclopentadienylzirconium X_(n),-   pentamethylcyclopentadienyltitanium X_(n),-   tetramethylcyclopentyltitanium X_(n),-   1,2,4-trimethylcyclopentadienylzirconium X_(n),-   dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2,3-trimethylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2-dimethylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(2-methylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(cyclopentadienyl)(indenyl)zirconium X_(n),-   dimethylsilyl(2-methylindenyl)(fluorenyl)zirconium X_(n),-   diphenylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(3-propylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(3-t-butylcyclopentadienyl)zirconium    X_(n),-   dimethylgermyl(1,2-dimethylcyclopentadienyl)(3-isopropylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(3-methylcyclopentadienyl)zirconium    X_(n),-   diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),-   diphenylmethylidene(cyclopentadienyl)(indenyl)zirconium X_(n),-   iso-propylidenebis(cyclopentadienyl)zirconium X_(n),-   iso-propylidene(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),-   iso-propylidene(3-methylcyclopentadienyl)(9-fluorenyl)zirconium-   ethylenebis(9-fluorenyl)zirconium X_(n),-   meso-ethylenebis(1-indenyl)zirconium X_(n),-   ethylenebis(1-indenyl)zirconium X_(n),-   ethylenebis(2-methyl-1-indenyl)zirconium X_(n),-   ethylenebis(2-methyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   ethylenebis(2-propyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   ethylenebis(2-isopropyl-4,5,6,7-tetrahydro-1-indenyl)zirconium    X_(n),-   ethylenebis(2-butyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   ethylenebis(2-isobutyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   dimethylsilyl(4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   diphenyl(4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   dimethylsilylbis(cyclopentadienyl)zirconium X_(n),-   dimethylsilylbis(9-fluorenyl)zirconium X_(n),-   dimethylsilylbis(1-indenyl)zirconium X_(n),-   dimethylsilylbis(2-methylindenyl)zirconium X_(n),-   dimethylsilylbis(2-propylindenyl)zirconium X_(n),-   dimethylsilylbis(2-butylindenyl)zirconium X_(n),-   diphenylsilylbis(2-methylindenyl)zirconium X_(n),-   diphenylsilylbis(2-propylindenyl)zirconium X_(n),-   diphenylsilylbis(2-butylindenyl)zirconium X_(n),-   dimethylgermylbis(2-methylindenyl)zirconium X_(n)-   dimethylsilylbis(tetrahydroindenyl)zirconium X_(n),-   dimethylsilylbis(tetramethylcyclopentadienyl)zirconium X_(n),-   dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),-   diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),-   diphenylsilylbis(indenyl)zirconium X_(n),-   cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium    X_(n),-   cyclotetramethylenesilyl(tetramethylcyclopentadienyl)(cyclopentadienyl)    zirconium X_(n),-   cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2-methylindenyl)zirconium    X_(n),-   cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(3-methylcyclopentadienyl)zirconium    X_(n),-   cyclotrimethylenesilylbis(2-methylindenyl)zirconium X_(n),-   cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2,3,5-trimethylcyclopentadienyl)zirconium    X_(n),-   cyclotrimethylenesilylbis(tetramethylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(tetramethylcyclopentadieneyl)(N-tert-butylamido)titanium    X_(n),-   bis(cyclopentadienyl)chromium X_(n),-   bis(cyclopentadienyl)zirconium X_(n),-   bis(n-butylcyclopentadienyl)zirconium X_(n),-   bis(n-dodecyclcyclopentadienyl)zirconium X_(n),-   bis(ethylcyclopentadienyl)zirconium X_(n),-   bis(iso-butylcyclopentadienyl)zirconium X_(n),-   bis(iso-propylcyclopentadienyl)zirconium X_(n),-   bis(methylcyclopentadienyl)zirconium X_(n),-   bis(n-oxtylcyclopentadienyl)zirconium X_(n),-   bis(n-pentylcyclopentadienyl)zirconium X_(n),-   bis(n-propylcyclopentadienyl)zirconium X_(n),-   bis(trimethylsilylcyclopentadienyl)zirconium X_(n),-   bis(1,3-bis(trimethylsilyl)cyclopentadienyl)zirconium X_(n),-   bis(1-ethyl-2-methylcyclopentadienyl)zirconium X_(n),-   bis(1-ethyl-3-methylcyclopentadienyl)zirconium X_(n),-   bis(pentamethylcyclopentadienyl)zirconium X_(n),-   bis(pentamethylcyclopentadienyl)zirconium X_(n),-   bis(1-propyl-3-methylcyclopentadienyl)zirconium X_(n),-   bis(1-n-butyl-3-methylcyclopentadienyl)zirconium X_(n),-   bis(1-isobutyl-3-methylcyclopentadienyl)zirconium X_(n),-   bis(1-propyl-3-butylcyclopentadienyl)zirconium X_(n),-   bis(1,3-n-butylcyclopentadienyl)zirconium X_(n),-   bis(4,7-dimethylindenyl)zirconium X_(n),-   bis(indenyl)zirconium X_(n),-   bis(2-methylindenyl)zirconium X_(n),-   cyclopentadienylindenylzirconium X_(n),-   bis(n-propylcyclopentadienyl)hafnium X_(n),-   bis(n-butylcyclopentadienyl)hafnium X_(n),-   bis(n-pentylcyclopentadienyl)hafnium X_(n),-   (n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafnium X_(n),-   bis [(2-trimethylsilylethyl)cyclopentadienyl]hafnium X_(n),-   bis(trimethylsilylcyclopentadienyl)hafnium X_(n),-   bis(2-n-propylindenyl)hafnium X_(n),-   bis(2-n-butylindenyl)hafnium X_(n),-   dimethylsilylbis(n-propylcyclopentadienyl)hafnium X_(n),-   dimethylsilylbis(n-butylcyclopentadienyl)hafnium X_(n),-   bis(9-n-propylfluorenyl)hafnium X_(n),-   bis(9-n-butylfluorenyl)hafnium X_(n),-   (9-n-propylfluorenyl)(2-n-propylindenyl)hafnium X_(n),-   bis(1-n-propyl-2-methylcyclopentadienyl)hafnium X_(n),-   (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium    X_(n),-   dimethylsilyl(tetramethyleyclopentadienyl)(cyclobutylamido)titanium    X_(n),-   dimethylsilyl(tetramethyleyclopentadienyl)(cyclopentylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclobutylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclopentylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium,    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclobutylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclopentylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium    X_(n),-   diphenylsilyl(tetramethyleyclopentadienyl)(n-octylamido)titanium    X_(n),-   diphenylsilyl(tetramethyleyclopentadienyl)(n-decylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium    X_(n),-   and derivatives thereof.

By “derivatives thereof”, it is meant any substitution or ring formationas described above; and in particular, replacement of the metal “M” (Cr,Zr, Ti or Hf) with an atom selected from the group consisting of Cr, Zr,Hf and Ti; and replacement of the “X” group with any of C₁ to C₅ alkyls,C₆ aryls, C₆ to C₁₀ alkylaryls, fluorine or chlorine; n is 1, 2 or 3.

It is contemplated that the metallocene catalysts components describedabove include their structural or optical or enantiomeric isomers(racemic mixture), and may be a pure enantiomer in one embodiment.

As used herein, a single, bridged, asymmetrically substitutedmetallocene catalyst component having a racemic and/or meso isomer doesnot, itself, constitute at least two different bridged, metallocenecatalyst components.

The “metallocene catalyst component” may comprise any combination of any“embodiment” described herein.

Activators

The catalyst system may also include one or more activators. As usedherein, the term “activator” is defined to be any compound orcombination of compounds, supported or unsupported, which can activate asingle-site catalyst compound (e.g., metallocenes, non-metallocenes,etc.), such as by creating a cationic species from the catalystcomponent.

In certain embodiments, either or both of the catalyst components may becontacted with a catalyst activator, herein simply referred to as an“activator.” Typically, this involves the abstraction of at least oneleaving group (X group in the formulas/structures above) from the metalcenter of the catalyst component. The catalyst components of the presentinvention are thus activated towards olefin polymerization using suchactivators. Embodiments of such activators include Lewis acids such ascyclic or oligomeric poly(hydrocarbylaluminum oxides) and so callednon-coordinating activators (“NCA”) (alternately, “ionizing activators”or “stoichiometric activators”), or any other compound that can converta neutral metallocene catalyst component to a metallocene cation that isactive with respect to olefin polymerization.

More particularly, it is within the scope of this invention to use Lewisacids such as alumoxane (e.g., “MAO”), modified alumoxane (e.g.,“TIBAO”), and alkylaluminum compounds as activators, and/or ionizingactivators (neutral or ionic) such as tri (n-butyl)ammoniumtetrakis(pentafluorophenyl)boron and/or a trisperfluorophenyl boronmetalloid precursors to activate desirable metallocenes describedherein. MAO and other aluminum-based activators are well known in theart. Ionizing activators are well known in the art and are described by,for example, Eugene You-Xian Chen & Tobin J. Marks, Cocatalysts forMetal-Catalyzed Olefin Polymerization: Activators, Activation Processes,and Structure-Activity Relationships 100(4) CHEMICAL REVIEWS 1391–1434(2000). The activators may be associated with or bound to a support,either in association with the catalyst component (e.g., metallocene) orseparate from the catalyst component, such as described by Gregory G.Hlatky, Heterogeneous Single-Site Catalysts for Olefin Polymerization100(4) CHEMICAL REVIEWS 1347–1374 (2000).

The aluminum alkyl (“alkylaluminum”) activator may be described by theformula AlR^(§) ₃, wherein R^(§) is selected from the group consistingof C₁ to C₂₀ alkyls, C₁ to C₂₀ alkoxys, halogen (chlorine, fluorine,bromine) C₆ to C₂₀ aryls, C₇ to C₂₅ alkylaryls, and C₇ to C₂₅arylalkyls. Non-limiting examples of aluminum alkyl compounds which maybe utilized as activators for the catalyst precursor compounds for usein the methods of the present invention include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like.

Examples of neutral ionizing activators include Group 13 tri-substitutedcompounds, in particular, tri-substituted boron, tellurium, aluminum,gallium and indium compounds, and mixtures thereof. The threesubstituent groups are each independently selected from alkyls,alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy andhalides. In one embodiment, the three groups are independently selectedfrom halogen, mono or multicyclic (including halosubstituted) aryls,alkyls, and alkenyl compounds and mixtures thereof. In anotherembodiment, the three groups are selected from alkenyl groups having 1to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxygroups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbonatoms (including substituted aryls), and combinations thereof. In yetanother embodiment, the three groups are selected from alkyls having 1to 4 carbon groups, phenyl, naphthyl and mixtures thereof. In yetanother embodiment, the three groups are selected from highlyhalogenated alkyls having 1 to 4 carbon groups, highly halogenatedphenyls, and highly halogenated naphthyls and mixtures thereof. By“highly halogenated”, it is meant that at least 50% of the hydrogens arereplaced by a halogen group selected from fluorine, chlorine andbromine. In yet another embodiment, the neutral stoichiometric activatoris a tri-substituted Group 13 compound comprising highly fluorided arylgroups, the groups being highly fluorided phenyl and highly fluoridednaphthyl groups.

In another embodiment, the neutral tri-substituted Group 13 compoundsare boron compounds such as a trisperfluorophenyl boron,trisperfluoronaphthyl boron, tris(3,5-di(trifluoromethyl)phenyl)boron,tris(di-t-butylmethylsilyl)perfluorophenylboron, and other highlyfluorinated trisarylboron compounds and combinations thereof, and theiraluminum equivalents. Other suitable neutral ionizing activators aredescribed in U.S. Pat. No. 6,399,532 B1, U.S. Pat. No. 6,268,445 B1, andin 19 ORGANOMETALLICS 3332–3337 (2000), and in 17 ORGANOMETALLICS3996–4003 (1998).

Illustrative, not limiting examples of ionic ionizing activators includetrialkyl-substituted ammonium salts such as triethylammoniumtetra(phenyl)boron, tripropylammonium tetra(phenyl)boron,tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron,tributylammonium tetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-tri-fluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boronand the like; N,N-dialkyl anilinium salts such as N,N-dimethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron and the like; dialkylammonium salts such as di-(isopropyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boronand the like; triaryl carbonium salts (trityl salts) such astriphenylcarbonium tetra(phenyl)boron and triphenylcarboniumtetra(pentafluorophenyl)boron; and triaryl phosphonium salts such astriphenylphosphonium tetra(phenyl)boron, triphenylphosphoniumtetra(pentafluorophenyl)boron, tri(methylphenyl)phosphoniumtetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boronand the like, and their aluminum equivalents.

In yet another embodiment of the activator of the invention, analkylaluminum can be used in conjunction with a heterocyclic compound.The heterocyclic compound includes at least one nitrogen, oxygen, and/orsulfur atom, and includes at least one nitrogen atom in a particularembodiment. The heterocyclic compound includes 4 or more ring members inone embodiment, and 5 or more ring members in another embodiment.

The heterocyclic compound for use as an activator with an alkylaluminummay be unsubstituted or substituted with one or a combination ofsubstituent groups. Examples of suitable substituents include halogen,alkyl, alkenyl or alkynyl radicals, cycloalkyl radicals, aryl radicals,aryl substituted alkyl radicals, acyl radicals, aroyl radicals, alkoxyradicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals,alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals,alkyl- or dialkyl-carbamoyl radicals, acyloxy radicals, acylaminoradicals, aroylamino radicals, straight, branched or cyclic, alkyleneradicals, or any combination thereof. The substituents groups may alsobe substituted with halogens, particularly fluorine or bromine,heteroatoms or the like.

Non-limiting examples of hydrocarbon substituents include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenylgroups and the like, including all their isomers, for example tertiarybutyl, isopropyl, and the like. Other examples of substituents includefluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl orchlorobenzyl.

In one embodiment, the heterocyclic compound is unsubstituted. Inanother embodiment one or more positions on the heterocyclic compoundare substituted with a halogen atom or a halogen atom containing group,for example a halogenated aryl group. In one embodiment the halogen isselected from chlorine, bromine and fluorine, and selected from fluorineand bromine in another embodiment, and the halogen is fluorine in yetanother embodiment.

Non-limiting examples of heterocyclic compounds utilized in theactivator of the invention include substituted and unsubstitutedpyrroles, imidazoles, pyrazoles, pyrrolines, pyrrolidines, purines,carbazoles, and indoles, phenyl indoles, 2,5-dimethylpyrroles,3-pentafluorophenyl pyrrole, 4,5,6,7-tetrafluoroindole or3,4-difluoropyrroles.

In one embodiment, the heterocyclic compound described above is combinedwith an alkylaluminum or an alumoxane to yield an activator compoundwhich, upon reaction with a catalyst component, for example ametallocene, produces an active polymerization catalyst. Non-limitingexamples of suitable alkylaluminums include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, tri-iso-octylaluminum, triphenylaluminum, andcombinations thereof.

Other activators include those described in WO 98/07515 such as tris(2,2′,2″-nonafluorobiphenyl) fluoroaluminate. Combinations of activatorsare also contemplated by the invention, for example, alumoxanes andionizing activators in combinations. Other activators includealuminum/boron complexes, perchlorates, periodates and iodates includingtheir hydrates; lithium (2,2′-bisphenyl-ditrimethylsilicate) 4THF;silylium salts in combination with a non-coordinating compatible anion.Also, methods of activation such as using radiation, electro-chemicaloxidation, and the like are also contemplated as activating methods forthe purposes of rendering the neutral bulky ligand metallocene-typecatalyst compound or precursor to a bulky ligand metallocene-type cationcapable of polymerizing olefins. Other activators or methods foractivating a bulky ligand metallocene-type catalyst compound aredescribed in for example, U.S. Pat. Nos. 5,849,852, 5,859,653 and5,869,723 and WO 98/32775.

In general, the activator and catalyst component(s) are combined in moleratios of activator to catalyst component from 1000:1 to 0.1:1, and from300:1 to 1:1 in another embodiment, and from 150:1 to 1:1 in yet anotherembodiment, and from 50:1 to 1:1 in yet another embodiment, and from10:1 to 0.5:1 in yet another embodiment, and from 3:1 to 0.3:1 in yetanother embodiment, wherein a desirable range may include anycombination of any upper mole ratio limit with any lower mole ratiolimit described herein. When the activator is a cyclic or oligomericpoly(hydrocarbylaluminum oxide) (e.g., “MAO”), the mole ratio ofactivator to catalyst component ranges from 2:1 to 100,000:1 in oneembodiment, and from 10:1 to 10,000:1 in another embodiment, and from50:1 to 2,000:1 in yet another embodiment. When the activator is aneutral or ionic ionizing activator such as a boron alkyl and the ionicsalt of a boron alkyl, the mole ratio of activator to catalyst componentranges from 0.5:1 to 10:1 in one embodiment, and from 1:1 to 5:1 in yetanother embodiment.

Spray Drying Process

Any spray-drying method known in the art may be used. For example, asuitable spray-drying method comprises atomizing a solution, suspensionor dispersion of the catalyst and/or the activator, optionally togetherwith a filler, and optionally with heating of the solution, suspensionor dispersion. Atomization is preferably done by passing the slurrythrough the atomizer together with an inert drying gas, i.e., a gaswhich is nonreactive under the conditions employed during atomization,such as nitrogen for example. An atomizing nozzle or a centrifugal highspeed disc can be employed to effect atomization, whereby there iscreated a spray or dispersion of droplets of the mixture. The volumetricflow of drying gas, if used, preferably considerably exceeds thevolumetric flow of the slurry to effect atomization of the slurry and/orevaporation of the liquid medium. Ordinarily the drying gas is heated toa temperature as high as about 160° C. to facilitate atomization of theslurry; however, if the volumetric flow of drying gas is maintained at avery high level, it is possible to employ lower temperatures.Atomization pressures of from about 1 psig to 200 psig are suitable.Some examples of suitable spray-drying methods include those disclosedin U.S. Pat. Nos. 5,290,745, 5,652,314, 4,376,062, 4,728,705, 5,604,172,5,306,350 and 4,638,029.

FIG. 1 is a schematic representation of an exemplary spray-dryingapparatus. Referring to FIG. 1, each mixture is drawn through siliconetubing from a reservoir attached at point C by a peristaltic pump D. Asthe mixture passes through nozzle F, it is mixed with atomizing nitrogengas, which enters the system at point E. The mist of catalystcomposition thus formed in the drying chamber G is then dried in thepresence of bath nitrogen gas, which enters the drying chamber at pointA. The bath nitrogen bath is heated by heater B before entering.Particles of unacceptably large diameter catalyst composition are notentrained in the nitrogen flow and drop into oversize collection pot H.The remainder of the catalyst composition continues through chamberoutlet I into the cyclone separator J, where the particulate catalystcomposition is disengaged from the gas stream and dropped into aremovable product collection pot K, from which the fully activatedcatalyst composition is recovered. The nitrogen gas is drawn through theaspirator L and removed from the system at point M.

Another type of suitable spray-drying method includes forming a liquidmixture of a nonvolatile materials fraction, a solvent fraction and atleast one compressed fluid; and spraying the liquid mixture at atemperature and pressure that gives a substantially decompressive sprayby passing the mixture through an orifice into an environment suitablefor forming solid particulates by solvent evaporation. Such a method isdisclosed in U.S. Pat. No. 5,716,558.

By adjusting the size of the orifices of the atomizer employed duringspray-drying, it is possible to obtain particles having desired averageparticle size, e.g., from about 5 micrometers to about 200 micrometers.The particles recovered from the spray-drying can optionally bedecarboxylated by heating the particles, e.g., as disclosed in U.S. Pat.No. 5,652,314.

Any solid particulate material which is inert to the other components ofthe catalyst system, and during subsequent polymerization, can beemployed as the filler. Such materials can be organic or inorganic.Suitable fillers include fumed silica, non-fumed silica, boron nitride,titanium dioxide, zinc oxide, polystyrene, and calcium carbonate. Fumedhydrophobic silica is preferred because it imparts high viscosity to theslurry and good strength to the spray-dried particles. For example,Gasil™ or Cabosil™ may be used. The particulate material employed asfiller should have an average particle size no greater than 50micrometers, preferably no greater than 10 micrometers. The particulatematerial employed as filler should be dry, i.e., free of absorbed water.

Sufficient filler is preferably employed to produce a slurry suitablefor spray-drying, i.e., a slurry containing such filler in an amount offrom 0 percent by weight to about 15 percent by weight, preferably fromabout 2.5 percent by weight to about 10 percent by weight. Whenspray-dried, such slurry produces discrete catalyst particles in whichfiller is present in an amount of from 0 percent by weight to about 50percent by weight, preferably from about 10 percent by weight to about30 percent by weight. The spray-dried catalyst particles produced inthis manner typically have an average particle size of from about 5micrometers to about 200 micrometers, preferably from about 10micrometers to about 30 micrometers.

Polymerization Process

The spray dried catalyst is suitable for use in any prepolymerizationand/or polymerization process over a wide range of temperatures andpressures. The temperatures may be in the range of from −60° C. to about280° C., preferably from 50° C. to about 200° C. In one embodiment, thepolymerization temperature is above 0° C., above 50° C., above 80° C.,above 100° C., above 150° C., or above 200° C. In one embodiment, thepressures employed may be in the range from 1 atmosphere to about 500atmospheres or higher.

Polymerization processes include solution, gas phase, slurry phase, anda high pressure process, or a combination thereof. Particularlypreferred is a gas phase or slurry phase polymerization of one or moreolefin(s) at least one of which is ethylene or propylene.

In one embodiment, the process is a solution, high pressure, slurry orgas phase polymerization process of one or more olefin monomers havingfrom 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and morepreferably 2 to 8 carbon atoms. The invention is particularly wellsuited to the polymerization of two or more olefin monomers of ethylene,propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octeneand 1-decene.

Other monomers useful include ethylenically unsaturated monomers,diolefins having 4 to 18 carbon atoms, conjugated or nonconjugateddienes, polyenes, vinyl monomers and cyclic olefins. Non-limitingmonomers useful in the invention may include norbornene, norbornadiene,isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkylsubstituted styrene, ethylidene norbornene, dicyclopentadiene andcyclopentene.

In another embodiment, a copolymer of ethylene is produced, where withethylene, a comonomer having at least one alpha-olefin having from 4 to15 carbon atoms, preferably from 4 to 12 carbon atoms, and mostpreferably from 4 to 8 carbon atoms, is polymerized in a gas phaseprocess.

In another embodiment, ethylene or propylene is polymerized with atleast two different comonomers, optionally one of which may be a diene,to form a terpolymer.

In one embodiment, the invention is directed to a polymerizationprocess, particularly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms.

Typically in a gas phase polymerization process, a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer.

The reactor pressure in a gas phase process may vary from about 100 psig(690 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in a gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C. In anotherembodiment, the reactor temperature in a gas phase process is above 60°C.

Other gas phase processes include series or multistage polymerizationprocesses. Gas phase processes may also include those described in U.S.Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, and European publicationsEP-A-0 794 200 EP-B1–0 649 992, EP-A-0 802 202 and EP-B-634 421.

In another embodiment, the process may produce greater than 500 lbs ofpolymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) orhigher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), morepreferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferablygreater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greaterthan 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greaterthan 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500Kg/hr).

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In another embodiment, the slurryprocess temperature is above 100° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers and oftenhydrogen along with catalyst are added. The suspension including diluentis intermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

In another embodiment, the polymerization technique is referred to as aparticle form polymerization, or a slurry process where the temperatureis kept below the temperature at which the polymer goes into solution.Such technique is well known in the art, and described in for instanceU.S. Pat. No. 3,248,179. Other slurry processes include those employinga loop reactor and those utilizing a plurality of stirred reactors inseries, parallel, or combinations thereof. Non-limiting examples ofslurry processes include continuous loop or stirred tank processes.Also, other examples of slurry processes are described in U.S. Pat. No.4,613,484.

In another embodiment, this process may produce greater than 2000 lbs ofpolymer per hour (907 Kg/hr), more preferably greater than 5000 lbs/hr(2268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540Kg/hr). In another embodiment the slurry reactor may produce greaterthan 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greaterthan 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500Kg/hr).

Examples of solution processes are described in U.S. Pat. Nos.4,271,060, 5,001,205, 5,236,998 and 5,589,555 and PCT WO 99/32525.

In one embodiment, the slurry or gas phase process is operated in thepresence of the catalyst system described herein and in the absence ofor essentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This process isdescribed in PCT publication WO 96/08520 and U.S. Pat. Nos. 5,712,352and 5,763,543.

In another embodiment, the method provides for injecting the catalystsystem described herein into a reactor, particularly a gas phasereactor. In one embodiment the catalyst system is used in theunsupported form, preferably in a liquid form such as described in U.S.Pat. Nos. 5,317,036 and 5,693,727 and European publication EP-A-0 593083. The polymerization catalyst in liquid form can be fed with anactivator, and/or a support, and/or a supported activator together orseparately to a reactor. The injection methods described in PCTpublication WO 97/46599 may be utilized.

Where an unsupported catalyst system is used the mole ratio of the metalof the activator component to the metal of the catalyst compound is inthe range of between 0.3:1 to 10,000:1, preferably 100:1 to 5000:1, andmost preferably 500:1 to 2000:1.

Polymer Products

The polymers produced can be used in a wide variety of products andend-use applications. The polymers produced include polyethylenehomopolymers and polyethylene co-polymers, including linear low densitypolyethylene, elastomers, plastomers, high density polyethylenes, mediumdensity polyethylenes, low density polyethylenes, as well aspolypropylene homopolymers and polypropylene co polymers.

The polymers, typically ethylene based polymers, have a density in therange of from 0.86 g/cc to 0.97 g/cc, preferably in the range of from0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/ccto 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to0.940 g/cc, and most preferably greater than 0.915 g/cc, preferablygreater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.Density is measured in accordance with ASTM-D-1238.

The polymers produced typically have a molecular weight distribution, aweight average molecular weight to number average molecular weight(M_(w)/M_(n)) of greater than 1.5 to about 15, particularly greater than2 to about 10, more preferably greater than about 2.2 to less than about8, and most preferably from 2.5 to 8. The polymers may have a narrowmolecular weight distribution and a broad composition distribution orvice-versa, and may be those polymers described in U.S. Pat. No.5,798,427.

Also, the polymers typically have a narrow composition distribution asmeasured by Composition Distribution Breadth Index (CDBI). Furtherdetails of determining the CDBI of a copolymer are known to thoseskilled in the art. See, for example, PCT Patent Application WO93/03093, published Feb. 18, 1993. The polymers in one embodiment haveCDBI's generally in the range of greater than 50% to 100%, preferably99%, preferably in the range of 55% to 85%, and more preferably 60% to80%, even more preferably greater than 60%, still even more preferablygreater than 65%. In another embodiment, polymers produced using acatalyst system described herein have a CDBI less than 50%, morepreferably less than 40%, and most preferably less than 30%.

The polymers in one embodiment have a melt index (MI) or (I₂) asmeasured by ASTM-D-1238-E (190/2.16) in the range from no measurableflow to 1000 dg/min, more preferably from about 0.01 dg/min to about 100dg/min, even more preferably from about 0.1 dg/min to about 50 dg/min,and most preferably from about 0.1 dg/min to about 10 dg/min.

In one embodiment, the polymers have a melt index ratio (I₂₁/I₂) (I₂₁ ismeasured by ASTM-D-1238-F) (190/21.6) of from 10 to less than 25, morepreferably from about 15 to less than 25. The polymers, in a preferredembodiment, have a melt index ratio (I₂₁/I₂) of from greater than 25,more preferably greater than 30, even more preferably greater that 40,still even more preferably greater than 50 and most preferably greaterthan 65. For example, the melt index ratio (I₂₁/I₂) may be of from 5 to300, 10 to 200, 20 to 180, 30 to 160, 40 to 120, 50 to 100, 60 to 90,and a combination of any upper limit with any lower limit.

In yet another embodiment, propylene based polymers are produced. Thesepolymers include atactic polypropylene, isotactic polypropylene,hemi-isotactic and syndiotactic polypropylene. Other propylene polymersinclude propylene block or impact copolymers. Propylene polymers ofthese types are well known in the art see for example U.S. Pat. Nos.4,794,096, 3,248,455, 4,376,851, 5,036,034 and 5,459,117.

The polymers may be blended and/or coextruded with any other polymer.Non-limiting examples of other polymers include linear low densitypolyethylenes, elastomers, plastomers, high pressure low densitypolyethylene, high density polyethylenes, polypropylenes and the like.

The polymers produced and blends thereof are useful in such formingoperations as film, sheet, and fiber extrusion and co-extrusion as wellas blow molding, injection molding and rotary molding. Films includeblown or cast films formed by coextrusion or by lamination useful asshrink film, cling film, stretch film, sealing films, oriented films,snack packaging, heavy duty bags, grocery sacks, baked and frozen foodpackaging, medical packaging, industrial liners, membranes, etc. infood-contact and non-food contact applications. Fibers include meltspinning, solution spinning and melt blown fiber operations for use inwoven or non-woven form to make filters, diaper fabrics, medicalgarments, geotextiles, etc. Extruded articles include medical tubing,wire and cable coatings, pipe, geomembranes, and pond liners. Moldedarticles include single and multi-layered constructions in the form ofbottles, tanks, large hollow articles, rigid food containers and toys,etc.

Bimodal Polymer Product

The polymers produced by the processes described herein, utilizing themixed catalysts described herein, are preferably bimodal. The term“bimodal,” when used to describe a polymer or polymer composition, e.g.,polyolefins such as polypropylene or polyethylene, or otherhomopolymers, copolymers or terpolymers, means “bimodal molecular weightdistribution,” which term is understood as having the broadestdefinition persons in the pertinent art have given that term asreflected in printed publications and issued patents. For example, asingle composition that includes polyolefins with at least oneidentifiable high molecular weight distribution and polyolefins with atleast one identifiable low molecular weight distribution is consideredto be a “bimodal” polyolefin, as that term is used herein. Preferably,other than having different molecular weights, the high molecular weightpolyolefin and the low molecular weight polyolefin are essentially thesame type of polymer, e.g., polypropylene or polyethylene.

The bimodal polymer products prepared using the mixed catalystsdescribed herein can be used in a wide variety of products and end-useapplications. The polymers produced by the process of the inventioninclude linear low density polyethylene, elastomers, plastomers, highdensity polyethylenes, low density polyethylenes, medium densitypolyethylenes, polypropylene and polypropylene copolymers.

Polymers that can be made using the described processes can have avariety of compositions, characteristics and properties. At least one ofthe advantages of the catalysts is that the process utilized can betailored to form a polymer composition with a desired set of properties.For example, it is contemplated that the polymers having the sameproperties as the bimodal polymer compositions in U.S. Pat. No.5,525,678 can be formed. Also, the bimetallic catalysts described hereincan be used in polymerization processes to form polymers having the sameproperties as the polymers in the following patents, U.S. Pat. Nos.6,420,580; 6,388,115; 6,380,328; 6,359,072; 6,346,586; 6,340,730;6,339,134; 6,300,436; 6,274,684; 6,271,323; 6,248,845; 6,245,868;6,245,705; 6,242,545; 6,211,105; 6,207,606; 6,180,735; and 6,147,173.

The polymers, typically ethylene based polymers, should have a densityin the range of from 0.86 g/cc to 0.97 g/cc, preferably in the range offrom 0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/ccto 0.955 g/cc, yet even more preferably in the range from 0.910 g/cc to0.955 g/cc, and most preferably greater than 0.915 g/cc, preferablygreater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.

The polymers can have a molecular weight distribution, a weight averagemolecular weight to number average molecular weight (M_(w)/M_(n)) ofgreater than 5 to about 80, particularly greater than 10 to about 60,more preferably greater than about 15 to less than about 55, and mostpreferably from 20 to 50.

The polymers made by the described processes can in certain embodimentshave a melt index (MI) or (I₂) as measured by ASTM-D-1238-E in the rangefrom 0.01 dg/min to 1000 dg/min, more preferably from about 0.01 dg/minto about 100 dg/min, even more preferably from about 0.02 dg/min toabout 50 dg/min, and most preferably from about 0.03 dg/min to about 0.1dg/min.

Polymers made by the described processes can in certain embodiments havea melt index ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of from40 to less than 500, more preferably from about 60 to less than 200.

Expressed differently, polymers made by the described processes can incertain embodiments have a melt index ratio (I₂₁/I₂) (I₂₁ is measured byASTM-D-1238-F) of from preferably greater than 40, more preferablygreater than 50, even more preferably greater that 60, still even morepreferably greater than 65 and most preferably greater than 70. In oneor more other embodiments, the polymer of the invention may have anarrow molecular weight distribution and a broad compositiondistribution or vice-versa, and may be those polymers described in U.S.Pat. No. 5,798,427.

In certain embodiments, propylene based polymers can be produced usingthe processes described herein. These polymers include atacticpolypropylene, isotactic polypropylene, hemi-isotactic and syndiotacticpolypropylene. Other propylene polymers include propylene block orimpact copolymers. Propylene polymers of these types are well known inthe art see for example U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851,5,036,034 and 5,459,117.

The polymers of the invention may be blended and/or coextruded with anyother polymer. Non-limiting examples of other polymers include linearlow density polyethylenes produced via conventional Ziegler-Natta and/orbulky ligand metallocene-type catalysis, elastomers, plastomers, highpressure low density polyethylene, high density polyethylenes,polypropylenes and the like.

Polymers produced by the process of the invention and blends thereof areuseful in such forming operations as film, sheet, pipe and fiberextrusion and co-extrusion as well as blow molding, injection moldingand rotary molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, membranes, etc. in food-contact and non-food contactapplications. Fibers include melt spinning, solution spinning and meltblown fiber operations for use in woven or non-woven form to makefilters, diaper fabrics, medical garments, geotextiles, etc. Extrudedarticles include medical tubing, wire and cable coatings, geomembranes,and pond liners. Molded articles include single and multi-layeredconstructions in the form of bottles, tanks, large hollow articles,rigid food containers and toys, etc.

EXAMPLES

In order to provide a better understanding of the foregoing discussion,the following non-limiting examples are offered. Although the examplesmay be directed to specific embodiments, they are not to be viewed aslimiting the invention in any specific respect. All parts, proportions,and percentages are by weight unless otherwise indicated. All exampleswere carried out in dry, oxygen-free environments and solvents. Allmolecular weights are weight average molecular weight unless otherwisenoted. Molecular weights including weight average molecular weight(M_(w)), number average molecular weight (M_(n)), and z-averagemolecular weight (Mz) were measured by Gel Permeation Chromatography(GPC), also known as size exclusion chromatography (SEC).

Example 1 (Comparative)

“HN3Zr”{Bis(phenylmethyl)[N′-(2,4,6-trimethylphenyl)-N-[2-[2,4,6-trimethylphenyl)amino-kN]ethyl]-1,2-ethanediaminato(2-)kN,kN′]zirconium} and “X”{(n-propylcyclopentadienyl)(tetramethylcyclopentadienyl) zirconiumdichloride} were mixed at a 4.5 to 1 molar ratio and then activated withmethyl alumoxane. This catalyst system was then supported on silicaCabosil TS 610 in a pilot scale spray dryer. The Cabosil TS 610 was soldby Cabot Corporation. The composition of the resulting spray driedcatalyst was 2 wt % HN3Zr/X, 32% methyl alumoxane, 66% cabosil TS610.

This catalyst was mixed with mineral oil (Hydrobrite® 550 manufacturedby Crompton Company) to produce three slurries having 8%, 12% and 18%solids concentration in oil. Foaming was noticed for each slurry and theintensity of foaming was found to increase with the solids concentrationof the slurry. The viscosity of each slurry was measured at 25° C. usinga Brookfield viscometer as a function of shear rate, and is reported inTable 1 below.

Example 2

The catalyst of Example 1 was mixed with Hydrobrite® 550 oil along with10% heptane to produce a slurry having 25% solids concentration. Eventhough the solids concentration was higher than the slurries of Example1, foaming was found to be significantly less. The viscosity of thisslurry was also measured using a Brookfield viscometer as a function ofshear rate and reported in Table 1.

TABLE 1 Effect of solids concentration on viscosity at 25° C. EX 1: EX.1: EX. 1: EX. 2: Viscosity Viscosity Viscosity Viscosity of 8% of 12% of18% of 25% Shear rate solids solids, solids solids (1/sec) (cP) (cP)(cP) (cP) 1.7 504 858 1014 402 3.4 453 762 990 411 5.1 442 724 980 4066.8 435 700 973 402 8.5 439 684 967 394 10.2 440 674 966 387 11.9 441668 962 379 13.6 439 658 958 375

As seen in Table 1, the viscosity of this slurry at 25% solids withheptane (Example 2) was less than the lower concentration slurrieswithout any heptane present. This observation was surprising andunexpected considering the Example 2 slurry contained as much as threetimes the amount of solids than the slurries of Example 1.

Example 3 (Comparative)

A spray dried catalyst containing “HN5Zr”{Bis(phenylmethyl)[N′-(2,3,4,5,6-pentamethylphenyl)-N-[2-[2,3,4,5,6-pentamethylphenyl)amino-kN]ethyl]-1,2-ethanediaminato(2-)kN,kN′]zirconium} and “X” {(n-propylcyclopentadienyl)(tetramethylcyclopentadienyl) zirconiumdichloride} were mixed at a 4.2to 1 molar ratio, and activated using methyl alumoxane. This catalystwas then supported on silica Cabosil TS 610 in a pilot scale spraydryer. This catalyst was then mixed with Hydrobrite® 550 mineral oil, toproduce a slurry having 18% solids concentration in oil. Significantfoaming was noticed.

Example 4

The catalyst of Example 3 was mixed with Hydrobrite® mineral oil toproduce a slurry having a higher solids concentration (25 wt %) alongwith 10% n-hexane. Again, foaming was significantly less. A side by sidecomparison showed a surprising reduction in the foam content of the 25%slurry with 10% hexane of Example 4 compared to the 18% slurry ofExample 3.

Example 5

A spray dried catalyst containing 2% by weight of HN5Zr/X mixed at 5:1molar ratio, 32% by weight of methyl alumoxane and 66% by weight ofCabosil TS 610 was prepared in a pilot scale spray dryer. The particlesize distribution of the catalyst as measured by Mastersizer Instrumentmade by Malvern Instruments Ltd, Malvern, U.K. is given below:

-   -   D90:42 micron;    -   D50:24 micron; and    -   D10:13 micron.

A large scale slurry was prepared using this catalyst and n-hexane andanother type of mineral oil (Kaydol® also manufactured by CromptonCompany) to test the foaming and ease of handling. The slurry was madein a 125 gallon vessel fitted with a helical ribbon agitator. About 483lbs. of degassed mineral oil was charged into the 125 gallon vessel, and71 lbs. of n-hexane was added and mixed for 1 hour at 40° C. Then 156.4lbs. of the spray dried catalyst was added over a period of two hours.The slurry in the 125 gallon vessel was mixed at 40° C. for about 4hours and discharged into a horizontal metal cylinder of 120 gallonsize. The composition of the slurry was 22% catalyst, 10% hexane, and68% oil.

There was no foaming observed. The solids were mixed well and dischargedinto the horizontal cylinder easily. The viscosity of the slurry wasmeasured using a Brookfield viscometer and the viscosity was much lowerthan the 18% slurry of Example 1. The results are shown in Table 2below.

TABLE 2 Viscosity of 22% slurry, 10% hexane and 68% oil (Kaydol ®) ShearRate (1/sec) Viscosity (cP) 1.40 600 2.80 564 4.20 524 5.60 492 7.00 4668.40 446 9.80 428 11.20 415

The above slurry was stored in the 125 gallon horizontal cylinder forabout 6 months at ambient temperature. After rolling the cylinder for 24hours, the slurry was transferred to a catalyst feeder in a fluidizedbed reactor. No problem in transfer was encountered. The slurry was fedto the fluidized bed reactor for about 15 hours and 80,000 lbs ofbimodal HDPE was produced. The properties of the resin were as follows:

-   -   Flow index: 8.5 dg/min;    -   Melt Flow Ratio: 218; and    -   Density: 0.9489.

Example 6

Another slurry using a different catalyst ratio (HN5Zr/X mixed at 5.5 to1 ratio) was prepared similar to the Example 5. No foaming or handlingproblem was encountered with this slurry (22% catalyst, 10% n-hexane and68% Kaydol® oil). The slurry was stored in the 125 gallon horizontalcylinder for about 9 months at ambient temperature. After rolling thecylinder for 24 hours, the slurry was transferred to a catalyst feederin a fluidized bed reactor. No problem in transfer was encountered. Theslurry was fed to the fluid bed reactor for about 15 hours and 80,000lbs of bimodal HDPE was produced. The properties of the resin were asfollows:

-   -   Flow index: 6.5 dg/min;    -   Melt Flow Ratio: 115; and    -   Density: 0.9481.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties, reaction conditions, and so forth, used in thespecification and claims are to be understood as approximations based onthe desired properties sought to be obtained by the present invention,and the error of measurement, etc., and should at least be construed inlight of the number of reported significant digits and by applyingordinary rounding techniques. Notwithstanding that the numerical rangesand values setting forth the broad scope of the invention areapproximations, the numerical values set forth are reported as preciselyas possible.

All priority documents are herein fully incorporated by reference forall jurisdictions in which such incorporation is permitted. Further, alldocuments cited herein, including testing procedures, are herein fullyincorporated by reference for all jurisdictions in which suchincorporation is permitted.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

1. A method for preparing a catalyst, comprising: first combiningmineral oil with one or more liquid alkanes having three or more carbonatoms to form a mixture; followed by combining with the mixture a spraydried catalyst system comprising one or more components selected fromthe group consisting of metallocenes, non-metallocenes, and acombination thereof to form a slurry.
 2. The method of claim 1, whereinthe viscosity of the slurry is reduced by at least 30 percent due to theaddition of the one or more liquid alkanes.
 3. The method of claim 1,wherein the catalyst system is a mixed catalyst system comprising atleast one metallocene component and at least one non-metallocenecomponent.
 4. The method of claim 1, wherein the slurry comprises up to20 percent by weight of the one or more liquid alkanes.
 5. The method ofclaim 1, wherein the slurry comprises between about 2 percent by weightand 15 percent by weight of the one or more liquid alkanes.
 6. Themethod of claim 1, wherein the slurry comprises up to 50 percent byweight of the catalyst system.
 7. The method of claim 1, wherein theslurry comprises at least 10 percent by weight of the catalyst system.8. The method of claim 1, wherein the slurry comprises from 5 percent byweight to about 35 percent by weight of the catalyst system.
 9. Themethod of claim 1, wherein the slurry comprises from 10 percent byweight to about 30 percent by weight of the catalyst system.
 10. Themethod of claim 1, wherein the metallocene, when present, is representedby the formula:Cp^(A)Cp^(B)MX_(n) wherein: M is a metal atom; Cp^(A) and Cp^(B) areeach independently an unsubstituted or substituted cyclic ring group; Xis a leaving group; and n is zero or an integer from 1 to
 4. 11. Themethod of claim 10, wherein Cp^(A) and Cp^(B) are each independentlyselected from the group consisting of cyclopentadienyl, indenyl,combinations thereof, and derivatives thereof.
 12. The method of claim10, wherein M is zirconium.
 13. The method of claim 10, wherein X isselected from the group consisting of amines, phosphones, ethers,carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbonatoms, hydrides, halogens, combinations thereof, and derivativesthereof, and wherein n is
 2. 14. The method of claim 1, wherein thenon-metallocene, when present, is represented by the formula:α_(a)β_(b)γ_(g)MX_(n) wherein M is a metal; X is independently selectedfrom the group consisting of halogen ions, hydrides, C₁ to C₁₂ alkyls,C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls, C₁ to C₁₂alkoxys, C₆ to C₁₆ aryloxys, C₇ to C₁₈ alkylaryloxys, C₁ to C₁₂fluoroalkyls, C₆ to C₁₂ fluoroaryls, C₁ to C₁₂ heteroatom-containinghydrocarbons, halogenated C₆ to C₁₆ aryloxys, and substitutedderivatives thereof; β and γ are groups that each comprise at least oneGroup 14 to Group 16 atom; α is a linking moiety that forms a chemicalbond to each of β and γ; and a, b, g, and n are each integers from 1 to4.
 15. The method of claim 14, wherein M is zirconium.
 16. A method forolefin polymerization, comprising: first combining mineral oil with oneor more liquid alkanes having three or more carbon atoms to form amixture; followed by combining with the mixture a spray dried catalystsystem comprising one or more catalysts selected from the groupconsisting of metallocenes, non-metallocenes, and a combination thereofto form a slurry; and transferring the slurry to a gas phase reactor;and thereby contacting the slurry with one or more olefin monomers,optionally, having 2 to 30 carbon atoms.
 17. The method of claim 16,wherein the viscosity of the slurry is reduced by at least 30 percentdue to the addition of the one or more liquid alkanes.
 18. The method ofclaim 16, wherein the catalyst system is a mixed catalyst systemcomprising at least one metallocene component and at least onenon-metallocene component.
 19. The method of claim 16, wherein theslurry comprises up to 20 percent by weight of the one or more liquidalkanes.
 20. The method of claim 16, wherein the slurry comprises up to50 percent by weight of the catalyst system.
 21. The method of claim 16,wherein the metallocene, when present, is represented by the formula:Cp^(A)Cp^(B)MX_(n) wherein: M is a metal atom; Cp^(A) and Cp^(B) areeach independently an unsubstituted or substituted cyclic ring group; Xis a leaving group; and n is zero or an integer from 1 to
 4. 22. Themethod of claim 21, wherein Cp^(A) and Cp^(B) are each independentlyselected from the group consisting of cyclopentadienyl, indenyl,combinations thereof, and derivatives thereof, and wherein M iszirconium.
 23. The method of claim 21, wherein X is selected from thegroup consisting of amines, phosphones, ethers, carboxylates, dienes,hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,halogens, combinations thereof, and derivatives thereof, and wherein nis
 2. 24. The method of claim 16, wherein the non-metallocene, whenpresent, is represented by the formula:α_(a)β_(b)γ_(g)MX_(n) wherein M is a metal; X is independently selectedfrom the group consisting of halogen ions, hydrides, C₁ to C₁₂ alkyls,C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls, C₁ to C₁₂alkoxys, C₆ to C₁₆ aryloxys, C₇ to C₁₈ alkylaryloxys, C₁ to C₁₂fluoroalkyls, C₆ to C₁₂ fluoroaryls, C₁ to C₁₂ heteroatom-containinghydrocarbons, halogenated C₆ to C₁₆ aryloxys, and substitutedderivatives thereof; β and γ are groups that each comprise at least oneGroup 14 to Group 16 atom; α is a linking moiety that forms a chemicalbond to each of β and γ; and a, b, g, and n are each integers from 1 to4.
 25. The method of claim 24, wherein M is zirconium.